CN102936742B - Method for electroplating black trivalent chromium on surface of plastic for vehicle decorating strip - Google Patents
Method for electroplating black trivalent chromium on surface of plastic for vehicle decorating strip Download PDFInfo
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- CN102936742B CN102936742B CN201210440818.6A CN201210440818A CN102936742B CN 102936742 B CN102936742 B CN 102936742B CN 201210440818 A CN201210440818 A CN 201210440818A CN 102936742 B CN102936742 B CN 102936742B
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- 239000011651 chromium Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 48
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000004033 plastic Substances 0.000 title claims abstract description 43
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 41
- 238000009713 electroplating Methods 0.000 title abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 199
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 97
- 238000007747 plating Methods 0.000 claims abstract description 77
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000004519 grease Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 64
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 23
- 239000004327 boric acid Substances 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 19
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 claims description 18
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 12
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 12
- 229940038773 trisodium citrate Drugs 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000001994 activation Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 239000004568 cement Substances 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 239000001488 sodium phosphate Substances 0.000 claims description 8
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 8
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 8
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 7
- 239000000080 wetting agent Substances 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229940085605 saccharin sodium Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- -1 sodium phenyl aldehyde Chemical class 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 230000003472 neutralizing effect Effects 0.000 abstract description 5
- 238000007788 roughening Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 2
- 239000000084 colloidal system Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 33
- 238000000576 coating method Methods 0.000 description 33
- 230000007613 environmental effect Effects 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides a method for electroplating black trivalent chromium on the surface of plastic for a vehicle decorating strip. The method includes the steps of surface roughening processing, surface neutralizing processing, surface activating treatment, surface accelerated processing, chemical nickel precipitating, plating bottom nickel, plating acid copper, sequentially plating semi-bright nickel, full-bright nickel and microporous nickel and plating the black trivalent chromium. According to the method, the surface of a plastic workpiece is subjected to processes of ultrasonic grease removing, roughening, neutralizing, colloid palladium activating, accelerating and the like, the foundation is established for subsequently plating copper, nickel and finally the black trivalent chromium, the process is stable, and the formula is reasonable. Besides, when the formula is selected, a plating solution which has small influence on the environment is used as far as possible, and the electroplating process is environment-friendly.
Description
Technical field
The present invention relates to electroplating technology field, particularly relate to the method for the black chromium of a kind of automotive trim strip plastic surface plating trivalent.
Background technology
Electroplating black chromium is a kind of special plating in chromium plating system, and black chromium, in the chromic acid with strong oxidizing property, obtains the chromium metal of disperse in chromium sesquioxide hydrate through strong electron exchange.Chromium metal forms the coating of built-in type, and this coating is dendritic structure, and crystallization is loosened, and all absorbs, cause coating to be black to incident light wave.Because the stability of black chromium coating is high, be widely used in the Application Areass such as automobile component, opticinstrument, photographic apparatus, weaponry.
Have plating decorations sexavalent chrome and plating decorations trivalent chromium at plastic surface in prior art, but plating sexavalent chrome coating skewness, bonding force is looked into, to environmental protection and human health damage larger.Automotive trim strip plastic surface of the prior art adopts the chromic technique of plating, as Chinese patent application (publication number is: CN102242384A): relate to a kind of process for plating trivalent chromium on surfaces of plastic, this technique comprises the surperficial grease of removing, surface microscopic roughening treatment, reduction treatment, colloidal palladium activation, dispergation process, plating chemical nickel, plating watt nickel, plates the steps such as bright copper, bright nickel plating, plating trivalent chromium.Although this technique by repeatedly processing plastic surface thus reaching stable, the uniform effect of coating before plating trivalent chromium.But before plating trivalent chromium, plastic surface process is not in place, causes that coating covering power is poor, the easy embrittlement of coating, work-ing life are short.
Summary of the invention
Technical problem to be solved by this invention is, for the above-mentioned deficiency of prior art, proposes a kind of method that plating performance is better, coating is stablized, the automotive trim strip plastic surface of environmental protection electroplates the black chromium of trivalent.
The technical scheme that the present invention solves the employing of its technical problem is, propose the method for the black chromium of a kind of automotive trim strip plastic surface plating trivalent, the method comprising the steps of:
A, by automotive trim strip plastic cement at sodium hydroxide NaOH, sodium carbonate Na
2cO
3with water glass Na
2siO
3in mixing solutions, grease is removed in cleaning, immerses chromic trioxide CrO after removing grease
3with sulfuric acid H
2sO
4carry out surface coarsening process in mixed solution, then put into hydrochloric acid soln and carry out surface neutralization, after neutralization, adopt colloidal palladium solution to carry out surface activation process, then at sulfuric acid H
2sO
4carry out surface in solution and accelerate process;
B, by the plastic cement after above-mentioned surface treatment containing sulfuric acid nickel
2sO
4, inferior sodium phosphate Na
2pO
3with Trisodium Citrate C
6h
5na
3o
7mixing solutions in carry out chemical sinking nickel, then containing aqueous sulfuric acid nickel
2sO
4-7H
2o, moisture nickelous chloride NiCl
2-6H
2o, boric acid H
3bO
3plating bottoming nickel is carried out in mixing solutions;
C, the plastic cement after above-mentioned process is put into copper sulfate CuSO
4with sulfuric acid H
2sO
4in mixing solutions, carry out acid coppering process, then carry out plating half light nickel, full light nickel and microporous nickel successively, plate half light nickel, full light nickel is the same with the main component of microporous nickel plating solution, be aqueous sulfuric acid nickel
2sO
4-7H
2o, moisture nickelous chloride NiCl
2-6H
2o and boric acid H
3bO
3mixing solutions;
D, last at trivalent chromium base chromium sulphate Cr
2(SO
4)
3, stablizer H
2siF
4, wetting agent CH
3(CH
2)
11sO
3na, boric acid H
3bO
3the black chromium of trivalent is plated in mixing solutions.
As preferably, each constituent concentration in the degrease mixing solutions described in steps A: the concentration of sodium hydroxide NaOH is 20 ~ 35g/L, sodium carbonate Na
2cO
3concentration be 20 ~ 38g/L, water glass Na
2siO
3concentration be 55 ~ 93g/L.
Surface degrease step can know greasy dirt and other impurity of automotive trim strip plastic surface, impels surface coarsening even, improves binding force of cladding material.
As preferably, the concentration of each component in the surface coarsening process mixed solution described in steps A: chromic trioxide CrO
3concentration be 120 ~ 280g/L, sulfuric acid H
2sO
4concentration be 210 ~ 340g/L; Further preferably, chromic trioxide CrO
3concentration be 150 ~ 230g/L, sulfuric acid H
2sO
4concentration be 210 ~ 270g/L.
Chromic trioxide CrO
3be the main salt in plating solution, deposit chromium metal and production chromium sesquioxide hydrate etc. by the mechanism of oxidation-reduction reaction and electron exchange at automotive trim strip plastic surface, coating is turned black.Chromic trioxide CrO
3considerable influence is had, if chromic trioxide CrO to the covering power of plating solution
3content is high, then covering power is strong, and crystallization is careful, but if chromic trioxide CrO
3too high levels, then can make the hardness of coating decline.
In addition, chromic trioxide CrO
3with sulfuric acid H
2sO
4can at corrosion automotive trim strip plastic surface to form micro-roughened surface at automotive trim strip plastic surface as etching reagent, " snap close effect " required during to guarantee electroless plating, improves the bonding force of automotive trim strip plastic surface and coating with this.But sulfate radical can reduce the color characteristics of coating, coating is turned to be yellow, in order to can reach corrosion automotive trim strip plastic surface and reduce harmful effect simultaneously, need the content of accurately configuration sulfuric acid.
As preferably, the concentration of hydrochloric acid solution of the surperficial neutralizing treatment described in steps A is 18 ~ 68g/L.
Surface neutralizing treatment mainly removes the sexavalent chrome produced in surface coarsening treating processes, prevents hexavalent chromium polluted subsequent technique.
As preferably, the concentration of each component in the colloidal palladium solution of the surface activation process described in steps A: Palladous chloride PdCl
2concentration be 1.1 ~ 1.9g/L, tin protochloride SnCl
2concentration be 1.2 ~ 4.5g/L; Further preferably, Palladous chloride PdCl
2concentration be 1.4 ~ 1.7g/L, tin protochloride SnCl
2concentration be 3.1 ~ 4.5g/L.
In colloidal palladium solution, Palladous chloride is covered in automotive trim strip plastic surface, for follow-up chemical nickel provides catalytic center, the tin ion of tin protochloride then can be deposited on around palladium ion with the group of chemical combination state, avoid palladium ion be oxidized in water or in air and come off, the life cycle of colloidal palladium solution can be increased.
As preferably, the sulfuric acid H of process is accelerated on the surface described in steps A
2sO
4strength of solution is 25 ~ 82g/L.
Surface is accelerated process and is referred to and utilize sulfuric acid to remove in colloidal palladium solution the tin protochloride be coated on around palladium, is come out by palladium metal particle, makes subsequent chemistry sink nickel technique more smooth and easy.
As preferably, each concentration of component in the chemical sinking nickel mixing solutions described in step B: sulfuric acid nickel
2sO
4concentration be 15 ~ 28g/L, inferior sodium phosphate Na
2pO
3concentration be 23 ~ 32g/L, Trisodium Citrate C
6h
5na
3o
7concentration be 11 ~ 24g/L; Further preferably, sulfuric acid nickel
2sO
4concentration be 22 ~ 28g/L, inferior sodium phosphate Na
2pO
3concentration be 23 ~ 27g/L, Trisodium Citrate C
6h
5na
3o
7concentration be 11 ~ 24g/L.
Chemical sinking nickel refers to and deposit the thin conductive layer of one deck in the palladium metal that automotive trim strip plastic surface has catalytic activity, is convenient to the various metal of follow-up plating.
In chemical sinking nickel process, single nickel salt provides nickel element; Inferior sodium phosphate is strong reductant, and it is by the nickel ion (Ni in single nickel salt
2+) be reduced into metallic nickel; Trisodium Citrate is buffer reagent, and it makes the reaction of inferior sodium phosphate reduced nickel ion more mild.In the present invention, adopt Trisodium Citrate as buffer reagent, instead of existing boric acid, Trisodium Citrate is more friendly and cost is lower to environment, and by test of the present invention, the buffering energy of Trisodium Citrate is also better than boric acid, and this mainly because there is citric acid freely in Trisodium Citrate, can provide hydrogen ion and hydroxide ion.
As preferably, each concentration of component in the mixing solutions of the plating bottoming nickel described in step B: aqueous sulfuric acid nickel
2sO
4-7H
2the concentration of O is 87 ~ 120g/L, moisture nickelous chloride NiCl
2-6H
2the concentration of O is 5 ~ 84g/L, boric acid H
3bO
3concentration be 64 ~ 79g/L; Further preferably, aqueous sulfuric acid nickel
2sO
4-7H
2the concentration of O is 94 ~ 110g/L, moisture nickelous chloride NiCl
2-6H
2the concentration of O is 51 ~ 84g/L, boric acid H
3bO
3concentration be 68 ~ 72g/L.
In chemical sinking nickel, automotive trim strip plastic surface is made to cover the nickel dam of the conduction of layer by redox reaction; And in plating bottoming nickel, then adopt electrochemical method in chemical nickel, plate one deck nickel, strengthen the electroconductibility of coating further.In this step, aqueous sulfuric acid nickel
2sO
4-7H
2o, moisture nickelous chloride NiCl
2-6H
2o provides nickel ion needed for electrochemical reaction.
As preferably, each concentration of component in the mixing solutions of the acid coppering described in step C: copper sulfate CuSO
4concentration be 85 ~ 116g/L, sulfuric acid H
2sO
4concentration be 65 ~ 85g/L.Further preferably, copper sulfate CuSO
4concentration be 110 ~ 116g/L, sulfuric acid H
2sO
4concentration be 65 ~ 80g/L.
The object of acid coppering utilizes the characteristic of copper sulfate to improve luminance brightness and the planarization of automotive trim strip plastic surface, and can also improve the toughness of coating entirety.This is because copper coating compares nickel coating and other metal plating, its ductility is better, and after therefore plating sour layers of copper, toughness and the Surface flat of overall coating are improved.
Plating successively half light nickel described in step C, full light nickel and microporous nickel: plate in the processing step of half light nickel, full light nickel and microporous nickel, the main component of plating solution is the same, and the concentration of each component is: aqueous sulfuric acid nickel
2sO
4-7H
2the concentration of O is 150 ~ 240g/L, moisture nickelous chloride Nicl
2-6H
2the concentration of O is 55 ~ 85g/L, boric acid H
3bO
3concentration be 1 ~ 3g/L; Wherein plate plating solution in half light nickel step and be also added with butynediol additive, plate plating solution in full light nickel and be also added with saccharin sodium additives, in plating microporous nickel, plating solution is also added with 2-sulfonic group sodium phenyl aldehyde additive.
Plate half light nickel, full light nickel is the same with solution composition in microporous nickel, additive is different, thus makes the coating structure of formation different, makes each step all play different effects.Particularly, plate half light nickel and refer to the nickel dam plating one deck half light at automotive trim strip plastic surface, half light nickel coating is columnar structure, can improve the corrosion stability of coating; And this layer of electronickelling has good Surface flat and low porosity.Plate full light nickel and refer to the nickel dam plating one deck entire bright at automotive trim strip plastic surface, full light nickel coating is laminate structure, can improve the luminance brightness of coating.Plating microporous nickel refers to and plates one deck uniformly containing the coating of numerous non-conductive particulate at automotive trim strip plastic surface, can disperse corrosion current, reduce corrosion electric current density, improve coating erosion resistance further.
In addition, in plating half light nickel, full light nickel and microporous nickel step, stablizer all have employed boric acid but not Trisodium Citrate in chemical sinking nickel and plating bottoming nickel step.This is because more pay close attention to the covering power of coating and the compactness of coating when plating half light nickel, full light nickel and microporous nickel step, in chemical sinking nickel and plating bottoming nickel step, nickel coating mainly helps out.In the plating solution, boric acid can not only play the effect of stablizer plating solution, and can improve covering power and the covering power of plating solution, improves compactness of electroplating.Therefore choosing of boric acid needs comprehensive consideration environmental factors and it is to the reclamation element of coating.
As preferably, each concentration of component in the plating trivalent black chromium mixing solutions described in step D: trivalent chromium base chromium sulphate Cr
2(SO
4)
3concentration be 85 ~ 165g/L, stablizer H
2siF
4concentration be 25 ~ 55ml/L, wetting agent CH
3(CH
2)
11sO
3the concentration of Na is 5 ~ 65ml/L, boric acid H
3bO
3concentration be 15 ~ 35g/L.Further preferably, trivalent chromium base chromium sulphate Cr
2(SO
4)
3concentration be 120 ~ 150g/L, stablizer H
2siF
4concentration be 25 ~ 50ml/L, wetting agent CH
3(CH
2)
11sO
3the concentration of Na is 27 ~ 65ml/L, boric acid H
3bO
3concentration be 15 ~ 35g/L.
In the black chromium step of plating trivalent, stablizer H
2siF
4for forming stable compound with trivalent chromium, if too high can the impact of its concentration walks, if too low, easily there is blackstreak at coating surface or causing color and luster uneven; Wetting agent CH
3(CH
2)
11sO
3na can reduce liquid phase and solid phase surface tension, improve and walk; Boric acid uses as buffer reagent, can also take into account stabilizer function.Trivalent chromium base chromium sulphate Cr
2(SO
4)
3there is provided trivalent chromic ion, be different from existing hexavalent chromium, trivalent chromic ion has characteristic that is nontoxic, environmental protection.
The present invention is by art breading such as automotive trim strip plastic workpiece surface ultrasonic wave grease removal, alligatoring, neutralization, colloidal palladium activation and acceleration, and for follow-up electro-coppering, nickel and the black chromium of final trivalent lay the first stone process stabilizing, formula rationally.In addition, the present invention selects the plating solution little to environmental influence when filling a prescription and choosing as far as possible, makes electroplating technology more environmental protection.Further, the present invention also had the step of plating half light nickel, full light nickel and microporous nickel before the black chromium of final plating trivalent, and make the final coating formed more stable, color and luster is smooth, even, longer service life.
Embodiment
Be below that specific embodiments of the invention are further described technical scheme of the present invention, but the present invention is not limited to these embodiments.
Automotive trim strip plastic cement of the present invention comprises the automotive trim strip plastic workpiece that the materials such as all kinds of ABS, PC, PP, PVC, PET are made.
The method that above-mentioned automotive trim strip plastic workpiece is electroplated the black chromium of trivalent comprises the steps:
(1) surperficial degrease: at sodium hydroxide NaOH, sodium carbonate Na
2cO
3and Na
2siO
3clean in mixing solutions.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table one:
Table one
(2) surface coarsening process: at chromic trioxide CrO
3with sulfuric acid H
2sO
4carry out in mixed solution.In this step, chromic trioxide CrO
3with sulfuric acid H
2sO
4concentration proportioning is in different embodiments in table two:
Table two
(3) surperficial neutralizing treatment: the automotive trim strip plastic cement after surface coarsening process is put into hydrochloric acid soln and carries out.In this step, hydrochloric acid soln at the concentration proportioning of different embodiment in table three:
Table three
(4) surface activation process: surface activation process adopts colloidal palladium solution, colloidal palladium Chlorine in Solution palladium PdCl
2with tin protochloride SnCl
2at the concentration proportioning of different embodiment in table four:
Table four
(5) process is accelerated on surface: at sulfuric acid H
2sO
4carry out in solution.In this step sulphuric acid soln at the concentration proportioning of different embodiment in table five:
Table five
(6) chemical sinking nickel: containing sulfuric acid nickel
2sO
4, inferior sodium phosphate Na
2pO
3with Trisodium Citrate C
6h
5na
3o
7carry out in mixing solutions.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table six:
Table six
(7) bottoming nickel is plated: containing aqueous sulfuric acid nickel
2sO
4-7H
2o, moisture nickelous chloride NiCl
2-6H
2o, boric acid H
3bO
3mixing solutions in carry out.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table seven:
Table seven
(8) acid coppering: at copper sulfate CuSO
4with sulfuric acid H
2sO
4carry out in mixing solutions.Copper sulfate CuSO
4with sulfuric acid H
2sO
4at the concentration proportioning of different embodiment in table eight:
Table eight
(9) half light nickel, full light nickel and microporous nickel is plated successively.Plate in the processing step of half light nickel, full light nickel and microporous nickel, the main component of plating solution is the same, is aqueous sulfuric acid nickel
2sO
4-7H
2o, moisture nickelous chloride NiCl
2-6H
2o and boric acid H
3bO
3mixing solutions, but in the processing step of plating half light nickel, full light nickel and microporous nickel, the additive of different step is different.Plate half light nickel, full light nickel and the microporous nickel concentration proportioning in different embodiment respectively in table nine, table ten and table ten one.
Table nine (plating half light nickel)
Table ten (plating full light nickel)
Table ten one (plating microporous nickel)
(10) the black chromium of trivalent is plated: at trivalent chromium base chromium sulphate Cr
2(SO
4)
3, stablizer H
2siF
4, wetting agent CH
3(CH
2)
11sO
3na, boric acid H
3bO
3carry out in mixing solutions.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table ten two:
Table ten two
Through all smooth exquisiteness of trivalent black chromium plating color of the automotive trim strip plastic surface that embodiment 1 to embodiment 5 obtains, there is not the phenomenon that variegated, colourity is uneven.And this coating is stable, firmly, work-ing life is longer.Further, the trade effluent environmental pollution that the inventive method produces is less, environmental protection and reduce the cost of factory's back segment process trade effluent.
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.
Claims (6)
1. a method for the black chromium of automotive trim strip plastic surface plating trivalent, the method comprising the steps of:
A, by automotive trim strip plastic cement at sodium hydroxide NaOH, sodium carbonate Na
2cO
3with water glass Na
2siO
3in mixing solutions, grease is removed in cleaning, immerses chromic trioxide CrO after removing grease
3with sulfuric acid H
2sO
4carry out surface coarsening process in mixed solution, then put into hydrochloric acid soln and carry out surperficial pickling, adopt colloidal palladium solution to carry out surface activation process after pickling, then at sulfuric acid H
2sO
4carry out surface in solution and accelerate process;
B, by the plastic cement after above-mentioned surface treatment containing sulfuric acid nickel
2sO
4, inferior sodium phosphate and Trisodium Citrate C
6h
5na
3o
7mixing solutions in carry out chemical sinking nickel, then containing aqueous sulfuric acid nickel
2sO
47H
2o, moisture nickelous chloride NiCl
26H
2o, boric acid H
3bO
3plating bottoming nickel is carried out in mixing solutions; In described chemical sinking nickel mixing solutions, each component and concentration thereof are: sulfuric acid nickel
2sO
4concentration be 15 ~ 28g/L, the concentration of inferior sodium phosphate is 23 ~ 32g/L, Trisodium Citrate C
6h
5na
3o
7concentration be 11 ~ 24g/L;
C, the plastic cement after above-mentioned process is put into copper sulfate CuSO
4with sulfuric acid H
2sO
4in mixing solutions, carry out acid coppering process, then carry out plating half light nickel, full light nickel and microporous nickel successively, plate half light nickel, full light nickel is the same with the main component of microporous nickel plating solution, be aqueous sulfuric acid nickel
2sO
47H
2o, moisture nickelous chloride NiCl
26H
2o and boric acid H
3bO
3mixing solutions; In the processing step of described plating half light nickel, full light nickel and microporous nickel, each component of plating solution and concentration thereof are: aqueous sulfuric acid nickel
2sO
47H
2the concentration of O is 150 ~ 240g/L, moisture nickelous chloride Nicl
26H
2the concentration of O is 55 ~ 85g/L, boric acid H
3bO
3concentration be 1 ~ 3g/L; Wherein plate plating solution in half light nickel step and be also added with butynediol additive, plate plating solution in full light nickel and be also added with saccharin sodium additives, in plating microporous nickel, plating solution is also added with 2-sulfonic group sodium phenyl aldehyde additive;
D, last at trivalent chromium base chromium sulphate Cr
2(SO
4)
3, stablizer H
2siF
4, wetting agent CH
3(CH
2)
11sO
3na, boric acid H
3bO
3the black chromium of trivalent is plated in mixing solutions; Each component in described plating trivalent black chromium mixing solutions and concentration thereof are: trivalent chromium base chromium sulphate Cr
2(SO
4)
3concentration be 85 ~ 165g/L, stablizer H
2siF
4concentration be 25 ~ 55ml/L, wetting agent CH
3(CH
2)
11sO
3the concentration of Na is 5 ~ 65ml/L, boric acid H
3bO
3concentration be 15 ~ 35g/L.
2. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1, is characterized in that: in the degrease mixing solutions described in steps A, each component and concentration thereof are: the concentration of sodium hydroxide NaOH is 20 ~ 35g/L, sodium carbonate Na
2cO
3concentration be 20 ~ 38g/L, water glass Na
2siO
3concentration be 55 ~ 93g/L.
3. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1 and 2, is characterized in that: in the surface coarsening process mixed solution described in steps A, each component and concentration thereof are: chromic trioxide CrO
3concentration be 120 ~ 280g/L, sulfuric acid H
2sO
4concentration be 210 ~ 340g/L.
4. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1 and 2, is characterized in that: in the colloidal palladium solution of the surface activation process described in steps A, each component and concentration thereof are: Palladous chloride PdCl
2concentration be 1.1 ~ 1.9g/L, tin protochloride SnCl
2concentration be 1.2 ~ 4.5g/L.
5. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1, is characterized in that: in the mixing solutions of the plating bottoming nickel described in step B, each component and concentration thereof are: aqueous sulfuric acid nickel
2sO
47H
2the concentration of O is 87 ~ 120g/L, moisture nickelous chloride NiCl
26H
2the concentration of O is 5 ~ 84g/L, boric acid H
3bO
3concentration be 64 ~ 79g/L.
6. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1, is characterized in that: in the mixing solutions of the acid coppering described in step C, each component and concentration thereof are: copper sulfate CuSO
4concentration be 85 ~ 116g/L, sulfuric acid H
2sO
4concentration be 65 ~ 85g/L.
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| CN201210440818.6A CN102936742B (en) | 2012-11-07 | 2012-11-07 | Method for electroplating black trivalent chromium on surface of plastic for vehicle decorating strip |
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| CN111910230B (en) * | 2020-07-15 | 2021-08-06 | 九牧厨卫股份有限公司 | Antibacterial black chromium surface coating and preparation method thereof |
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